Ncx - - cc



United States Patent 25,371 CHLOROCYANOALKYL SILANES AND SILOXANESEnrico J. Pepe, Kenmore, N.Y., assignor to Union Carbide Corporation, acorporation of New York No Drawing. Original No. 2,985,679, dated May23, 1961, Ser. No. 831,047, Aug. 3, 1959. Application for reissue Sept.4, 1962, Ser. No. 222,261

11 Claims. (Cl. 260448.8)

NC(C H CI (1) wherein (a) is an integer of from 2 to 12, (b) is aninteger, (c) is an integer of at least 1, and the sum of (b+c) is equalto 2a and the organosilicon compound is selected from the classconsisting of 1) organosilanes having at least one valence of silicon,other than the valences satisfied by the chloro-cyanoalkyl group,satisfied by a halogen atom or an alkoxy group, the remaining valencesof silicon being satisfied by methyl groups or phenyl groups and (2)organosiloxanes having all of the valences of the silicon atomcontaining the chloro-cyanoalkyl group, other than the valencessatisfied by said chloro-cyanoalkyl group and by siloxane linkagessatisfied by methyl or phenyl groups and all remaining valences ofsilicon of said organosiloxane other than the silicon containing saidchloro-cyanoalkyl group, satisfied by monovalent hydrocarbon groups. Thecompositions of this invention are hereinafter referred to aschlorocyanoalkylsilicon compounds.

Thus, the chloro-cyanoalkylsilicon compounds of this invention includemonomeric silanes and polymeric siloxanes.

The monomeric organosilanes of this invention are thechlorocyanoalkylsilanes represented by the formula:

wherein (a), (b) and (c) have the above-defined meanings, R is a methylor a phenyl group, X is chlorine, fluorine or alkoxy groups, (n) is aninteger of from 1 to 3, (In) is an integer of from O to 2 and the sum of(n) and (In) is from 1 to 3. Illustrative of thechloro-cyanoalkylsilanes of the invention are2-chloro-2-cyanoethyltrichlorosilane,2,2-dichloro-2-cyanoethyltriethoxysilane, 2- chloro 2cyanopropyltrifluorosilane, 3,3 dichloro 3- cyanopropyltrichlorosilaneand the like; di(2-chloro-2- cyanoethyl) dichlorosilane, di2,2-dichloro-2-cyanoethyl) diethoxysilane, 3-chloro 3cyanopropylrnethyldichlorosilane, 3-chloro 3cyanopropylmethyldifluorosilane and the like; tri(2 chloro 2cyanoethyl)chlorosilane, 2- chloro 2 cyanopropyldimethylfluorosilane, 3chloro-Z- cyanopropyldiethylethoxysilane and the like. Examples of thealkoxy groups that are represented by X are methoxy, ethoxy, propoxy,butoxy, stearoxy and the like.

Re. 25,371 Reissued Apr. 16, 1963 The polymeric siloxanes of thisinvention include those organosiloxanes containing units of formula:

t wherein R, (a), (b), (c), (m) and (n) have the abovedefined meanings.These polymeric siloxanes include the trifunctional siloxanes,difunctional siloxanes and monofunctional siloxanes. The monofunctionalsiloxanes of this invention are those having units of the above formulawhere the sum of (n) and (m) is three. These mono functional siloxanesare, for example, bis-(2-chloro-2 cyanoethyl)tetramethyl disiloxane,tetra (2 chloro 2- cyauoethyhdimethyl disiloxane,heXa-(2-chl0ro-2-cyanopropyl) disiloxane and the like. The difunctionalsiloxanes of this invention are those having units of formula (3) Wherethe sum of (n) and (In) is two and includes linear siloxanes having anumber of such units, for eX- ample, 2 chloro 2cyanoethylmethylpolysiloxane, 3- chloro-3-cyanopropylphenylpolysiloxane,3,3 dichloro-3- cyanopropylmethylpolysiloxane,3-chl0ro-2-cyanopropylmethylpolysiloxane and the like. The difunctionalsiloxanes also include cyclic siloXanes having from 3 to 7 of suchunits, for example, tri(2-chloro-2-cyanoethyl)trimethylcyclotrisiloxane,tetra(3-chloro 3 cyanopropyl)- tetraphenylcyclotetrasiloxane,tetra(2,2-dichloro-2-cyanoethyl)tetrarnethylcyclotetrasiloxane, penta (3chloro-3- cyanopropyl)pentarnethylcyclopentasiloxane and the like. Thetrifunctional siloxanes of this invention are those having units ofFormula 3 when (n) equals 1 and (m) is zero and are, for example,3-cyano-3-chloropropylpolysiloXane,3,3-dichloro-3-cyanopropylpolysiloxane and the like.

The polymeric siloxanes of this invention also include those having atleast one unit of the Formula 3, and one or more siloxane units depictedby the formula:

R 1SiO T (4) wherein R is a monovalent hydrocarbon radical, (d) is aninteger of from 0 to 3 and (d) need not have the same value throughoutthe same molecule, and R can represent the same or diiferent groupswithin the same molecule. Illustrative of the monovalent hydrocarbonradicals that R can represent are alkyl groups such as methyl, ethyl,butyl and the like; alkenyl groups such as vinyl, aliyl and the like;aryl groups such as phenyl, naphthyl and the like; aralkyl such asphenylethyl and the like; and alkaryl such as tolyl and the like. Thepolymeric organosiloxanes include end-blocked linear polymericorganosiloxane oils, cyclic organosiloxanes, and resinousorganosiloxanes containing the same or different substituted mono-,diand trifunctional silicon atoms.

In accordance with my invention, the new compounds thereof are preparedby the chlorination of cyanoalkylhalosilanes of the formula:

m (NO-C aHZa) n l 4(n+m) Where R, (a), (m) and (n) are as above definedand Y is chlorine or fluorine, with gaseous chlorine in the presence ofultraviolet light and hydrogen chloride. The overall reaction can bedepicted by the following equation which, for the purpose ofillustration, depicts the chlorination of3-cyanopropylrnethyldichlorosilane:

(B) 01 on3 I have found that if the cyanoalkylchlorosilane is nottreated with hydrogen chloride gas prior to the addition of thechlorine, no chlorination takes place. The temperature at which thecyanoalkylchlorosilane is treated with hydrogen chloride is not narrowlycritical and can vary from :as low as C. to as high as 80 C. However, itis preferred to carry out the treatment with hydrogen chloride at atemperature from about 25 C. to about 40 C. so as to insure that thecyanoalkylchlorosilane will contain from about 1% to 10% by weighthydrogen chloride, at the temperature of chlorination. It is preferredthat the cyanoalkylchlorosilane contain from 2 to 5% hydrogen chlorideby weight. Although some of the cyanoalkylchlorosilanes are normallysolid at room temperatures once melted they do not recrystalize rapidlyand small amounts of impurities such as hydrogen chloride prevent thecrystallization of the cyanoalkyl chlorosilanes at lower temperatures.Thus, for example, it is possible to melt 2-cyanoethyltrichlorosilane,charge it into a flask, cool the flask and contents to a temperaturebelow the melting point and bubble dry hydrogen chloride into the liquidwithout recrystallization of the Z-cyanoethyltrichlorosi'lane.

The temperature at which the chlorination is accom plished is notnarrowly critical and can be from about 0 C. to about 150 C. However, Iprefer to conduct the chlorination at a temperature of from about 20 C.to about 80 C.

I have also found that unless the reaction is conducted in the presenceof ultra violet light, the chlorination as depicted in Equations A and Bdoes not take place. I have also found that diffuse sunlight issufficient to initiate the chlorination.

The process of this invention may be conducted under widely varyingconditions. Thus, the present process may be conducted as a vapor phasereaction or it may be conducted as a liquid phase reaction. It ispreferred to conduct the reaction as a liquid phase reaction, i.e.,bubbling chlorine gas into the liquid cyanoalkylchlorosilanehydrogenchloride solution.

The rate at which the chlorine gas is introduced into the solution isnot narrowly critical; however, I prefer to control the rate of theintroduction of the chlorine gas so that the temperature of the reactiondoes not exceed the preferred temperature of reaction given above andalso to prevent excessive foaming.

As can be seen by Equation A, one mole of chlorine is required to reactin order to introduce a chlorine radical into the cyanoalkylsilane.Furthermore, the introduction of a chlorine radical into the cyanoalkylgroup of the cyanoalkylsilane renders the carbon atom containing saidchlorine radical more readily susceptible to further chlorination. Thus,if highest conversions of the cyanoalkylsilanes tochlorocyanoalkylsilanes are to be obtained at least 2 moles of chlorineshould be employed for each equivalent cyanoalkyl group present (i.e.for monocyanoalkylsilanes at least 2 moles of chlorine per mole of thecyanoalkylsilane, for dicyanoalkylsilanes at least 4 moles of chlorinefor each mole of the dicyanoalkylsilane, etc.) Of course greater orlesser amounts of chlorine may be employed but no commensurateadvantages are obtained thereby.

The chlorocyanoalkylchlorosilanes of this invention can be esterifiedaccording to known procedures as, for example, by direct esterificationwith an alcohol, to yield the corresponding chlorocyanoalkylsilaneesters. Thus, the chlorocyanoalkylchlorosilanes can be esterified witharomatic alcohols such as phenol, benzyl alcohol and the like, andaliphatic alcohols such as methyl, ethyl, butyl, stearyl and the like.It is preferred to employ the aliphatic alcohols having from 1 to 4carbon atoms for economic reasons. In the esterifioation reaction it isdesired to minimize the formation of hydrogen chloride to keep theconcentration at minimum to prevent undesirable side reactions such asthe hydrolysis of the cyano group to a carbalkoxy group. Instead ofemploying an alcohol as the esterifying reagent, the formation ofhydrogen chloride can be minimized by employing a trialkyl orthoformateas the esterifying reagent. The concentration of hydrogen chloride canalso be kept at a minimum when an alcohol is employed as the esterfyingagent through the use of a hydrogen chloride acceptor such as pyridine,quinoline, triethylamine, tri-nbutylamine and the like.

The chlorocyanoalkylsilanes of this invention can be hydrolyzed andcondensed or the chlorocyanoalkylsilanes of this invention can becohydrolyzed and cocondensed with alkoxyor halosilanes of the formulawherein R, X and d are as above defined to yield the polymeric siloxanesof this invention.

The hydrolysis and condensation or cohydrolysis and co-condensation ofthe chlorocyanoalkylsilanes of this invention can be accomplished byknown methods such as, for example, adding IE1chlorocyanoalkylhalosilane to a mixture of diethyl ether and ice. It isnecessary to keep the concentration of the liberated hydrogen chlorideat a minimum in order to prevent undesirable side reactions such ashydrolysis of the cyano group to a carboxy group. If achlorocyanoalkylalkoxysilane of this invention is employed in thehydrolysis it is preferred that the concentration of any acidic or basiccatalyst employed be kept at a minimum to prevent side reactions.

The hydrolysis and condensation may be conducted according to thefollowing general procedure:

The chlorocyanoalkylalkoxysilane is added slowly with rapid stirring towater which contains an acidic or basic catalyst. The siloxane thusformed is extracted with a non-water miscible liquid organic solvent andthe solvent solution is washed with water until the water washings areneutral to litmus paper. The solvent is then removed by vacuumevaporation leaving as a residue the chlorocyanoalkylsiloxanes. Thealkoxy or halosilanes of Formula 5 above also can be cohydrolyzed andco-condensed with the chlorocyanoalkylsilanes by the above procedure toyield siloxanes.

A solvent is not necessary during the hydrolysis described above;however, a solvent may be employed as desired. Suitable solvents are,for example, isopropyh ether, diethylether and the like; toluene,benzene and the like; and the diethers of ethylene glycol andpolyethylene glycol and the like; and alcohols such as methanol, ethanoland the like.

The temperature at which the hydrolysis is conducted is not narrowlycritical and can be from 0 C. to 0; however, temperatures of from about0 C. to about 70 C. are preferred so as to give a reasonable rate ofhydrolysis and to minimize side reactions.

Catalysts that are useful in the hydrolysis of thechlorocyanoalkylalkoxysilanes of this invention are the acids or bases.Suitable acid catalysts are, for example, hydro chloric acid, sulfuricacid, oxalic acid, trifluoracetic acid, acetic acid and the like.Suitable basic catalysts are, for example, sodium hydroxide, potassiumhydroxide, ammonium hydroxide and the like. The concentration of thecatalyst is not narrowly critical and can be from 0.001 N to about 2.0 Nor even higher. The concentration of the catalyst is preferably keptbelow 1.0 N in order to prevent undesirable side reactions.

The cyanoalkylsilicon compounds that are useful as starting materials[isl in the preparation of the chlorocyanoalkylsilicon compounds of thisinvention [and] are the cyanoalkylhalosilanes having the formula m (NO-CnHzs) uS i--Y4- n+m R, (a), (n) and (m) are as above defined and Y ischlorine or fluorine. Such cyanoalkylchlorosilanes are, for example,2-cyanoethyltrichlorosilane, Z-cyanoethyltrifluorosilane, 3cyanopropylmethyldichlorosilane, 4- cyanobutyltrifluorosilane, 2cyanopropylmethyltrifluorosilane, 4 cyanobutyldimethylchlorosilane, 11cyanoundecyltrichlorosilane, di(2-cyanopropyl)dichlorosilane and thelike. Such [cyanoalkylchlorosilane] cyan alkylchlorosilanes are preparedby the reaction of an unsaturated nitrile with a silane containing asilicon bonded hydrogen atom in the presence of a catalyst such asplatinum.

I have also found that high conversions of the cyanohalosilanes tochlorinated cyanoalkylhalosilanes can be obtained by an alternateprocess which comprises reacting chlorine with the2-cyanoalkylhalosilane in the presence of ultra-violet light and ferricchloride at elevated temperatures.

The temperature at which the chlorination of the alternate process isconducted can vary from about 100 C. to about 145 C. It is preferredthat the temperature of the reaction be maintained at from about 130 C.to about 140 C.

The amount of ferric chloride catalyst employed in the alternate processof this invention is not narrowly critical. It is preferred to employfrom 0.5 to 2.0 parts ferric chloride per 100 parts of theZ-cyanopropylchlorosilane to be chlorinated.

The rate at which the chlorine is introduced into theZ-cyanopropylchlorosilane is not critical; however, I we fer to controlthe rate of the introduction of the chlorine gas so that the temperatureof the reaction remains at from 120 C. to about 145 C.

In the isolation of the chlorocyanoalkylsilicon compounds of thisinvention, particularly the chlorocyanoalkylchlorosilanes it isdesirable to distill the reaction products at reduced pressures in orderto reduce undesir able side reactions such as cleavage of the C-Si bond,dehydrohalogenation and dechlorination. The reduced pressure isolationis particularly useful in the isolation of chlorocyanoethylchlorosilanessince the chlorocyanoethylchlorosilanes undergo spontaneousdehydrohalogenation it heated to from about 120 C. toj250 C. atatmospheric pressure.

The chlorocyanoalkylsiloxanes of this invention are useful as lubricantsfor steel on steel either alone or in a mixture with other siloxanes.The chlorocyanoalkylsilanes can be hydrolyzed tochlorocyanoalkylsiloxanes which are useful as protective and decorativecoatings. The difunctional chlorocyanoalkylsiloxanes can be compoundedwith a silica filler and 'benzoyl peroxide and cured to tough, stretchyelastomers.

EXAMPLE 1 Into a 500 ml., 3-necked flask fitted with thermometer, watercondenser and fritted-glass, gas inlet tube were placed2-cyanopropyltrichlorosilane,

(235 g., 1.16 moles) and FeCl;; -7 g-, 2 Wt.-percent).

Calc. for C H SiNCl 20.3% C; 2.1% H; 11.8% Si; 5.9% N; 59.8% C1. Found:21.4% C; 2.3% H; 12.5% Si; 6.8% N; 59.2% CI.

The structure of the 2-chloro-2-cyanopropyltrichlorosilane was verifiedby infrared analysis. Other [chlorined] chlorinated derivatives of2-cyanopropyltrichlorosilane were isolated in an impure state.

EXAMPLE 2 A 3-liter, three-necked Pyrex flask was equipped with afritted glass gas difluser, low temperature condenser cooled with solidcarbon dioxide and a thermometer. 2-cyanoethyltrichlorosilane (2570 gm.13.6 moles) was charged into the flask and treated with dry hydrogenchloride gas at room temperature and atmospheric pressure. Anultraviolet light source was directed on the contents of the flask.Chlorine gas was bubbled in the mixture for 6 hours at such a rate as tomaintain the reaction temperature between 7080 C. At the end of thisperiod nitrogen was bubbled through the mixture for 1 hour to removedissolved hydrogen chloride and chlorine. A weight increase of 459 g.was observed (equivalent to 13.3 moles of Cl). Said increase in weightbeing due to the reaction of the chlorine with the -2-cyanoethyltrichlorosilane.

The reaction material subjected to fractional distillation under reducedpressure gave the compound Z-cyano- 2-chloroethyltrichlorosilane(NCCHC1CH SiCl in approximately 5 wt.-percent yield; B.P. 98/13 mm. Hg.

Calc. for C H SiCl N 63.6% hydrolyzable chlorine. Found: 63.1%hydrolyzable chlorine.

EXAMPLE 3 Into a 1-liter, 3-necked flask fitted with gas delivery tube,condenser, and thermometer was placed 3-cyanopropylmethyldichlorosilane(NC(CH Si(CH )Cl (500 g. 2.75 moles). The chlorosilane was cooled to +5C. with an ice bath and HCl gas bubbled in until the chlorosilaneappeared saturated (15 min.). Ultra-violet light was directed on thecontents of the flask and chlorine gas was bubbled into the reactionmixture at moderate rate (about 1 g./minute) for 2.5 hr. The temperaturerose to 50 C. in 2 hours. The reaction mixture was purged with'nit-rogento remove dissolved gases and weighed. A gain in weight of 72 g. wasobserved with the weight gain being due to the amount of chlorinereacted. The reaction mixture (570 g.) was charged to a 1-literdistillation flask and distilled through a Vigreaux column at reducedpressure; two fractions were obtained, the first, 413.0 g., B.P. -95/1.2mm. Hg; n 14728-14800; percent hydrolyzable Cl, 32.032.8; the second, 85g., B.P. /1.2 to 89/ 0.4 mm. Hg; 11 l.48121.4901; percent hydrolyzableCI, 26.3. Infrared survey and the determination of hydrolyzable chlorineindicated fraction 1 to be predominantly 3 chloro 3cyanopropylmethyldichlorosilane (NCCHCl-(CH Si(CH )C1 and fraction 2 tobe predominantly 3,3-dichloro-3-cyanopropylmethyldichlorosilane (NCCCl(CH Si(CH )C1 Both fractions were contaminated with the startingmaterial. Redistillation of fraction 1 yielded3-chloro-3-cyanopropylmethyldichlorosilane NCCHCl-(CH Si(CH )C1 B.P.104/4.0 mm. Hg, n 1.4788; percent hydrolyzable Cl, 32.7 (theory, 32.7).

EXAMPLE 4 Into a 1-liter, 3-necked flask fitted with thermometer,stirrer, and dropping funnel was placed2-chloro-2-cyanopropyltrichlorosilane, CH CCl(CH) CH SiCl (129 g. 0.54mole). Triethylorthoformate (240 g., 1.62 moles) was added over 0.5 hr.at room temperature (about 25 C.) with rapid stirring. The mixture wasstirred an additional one hour then heated to 80 C. for one hour. Lowboiling materials (efhylchloride, ethanol, ethylformate, etc.) wereremoved by vacuum stripping. The product 2-cyano-2-chloropropyltriethoxysilane was obtained in 90 mole-percentyield by distillation at reduced pressure (B.P. 53 C./0.03 mm. Hg n1.4200; d 1.04 g./cc.).

Calc. for C H SiO NCl: 45.2% C; 7.6% H; 10.6% Si; 5.3% N; 51.0% OC HFound: 47.6% C; 7.9% H; 11.4% Si; 4.8% N; 51.0% OC H The structure wasverified by infrared analysis.

EXAMPLE 5 Into a 500 ml. flask, fitted with a gas inlet tube, a gasoutlet tube and a thermometer, was charged liquid 2-cyanoethyltrichlorosilane (205 g., 1.09 mole). Anhydrous hydrogenchloride was bubbled into the liquid 2- cyanoethyltrichlorosilane forminutes at room temperature.

Chlorine gas was then bubbled into the2-cyanoethyltrichlorosilane-hydrogen chloride mixture for 2 hours whilethe temperature was maintained at 55 C. The reaction was thendiscontinued and nitrogen bubbled through the reaction mixture to removedissolved hydrogen chloride and unreacted chlorine. The reaction mixturewas then distilled at reduced pressure (less than 5 Hg) to yieldunreacted starting material and a fraction (B.P. 846 C. at 0.9 mm. Hg)identified as being a mixture of polychlorinated derivatives of2-cyanoethy1- trichlorosilane. Heating of the reaction mixture to-about185 C. resulted in dechlorination and dehydrochlorination of thechlorinated derivatives to yield 2-chloro-2- cyanovinyltrichlorosilane(B.P. 181 C. n 1.4897).

EXAMPLE 6 The products obtained by the chlorination of3-cyanopropylmethyldichlorosilane NC-(CI-I SiCH Cl prepared as inExample 3 (497 g.) were charged into a 3- lite-r, 3-necked flask fittedwith stirrer, dropping funnel, thermometer, and condenser.Triethylorthoformate (697 g., 4.7 moles) was added at room temperatureover 1.5 hr. with vigorous stirring. The mixture was heated to 80 C. for1 hour. The low boiling materials formed in the esterification such asethylchloride, ethylformate and the like were removed at reducedpressure. The reside was distilled at atmospheric pressure to yieldfraction 1 (226 g.) B.P. 84-98/4 mm. Hg, 11 1.4271.

Infra-red and elemental analysis indicate that fraction 1 is a mixtureof B-cyanopropylmethyldiethoxysilane (NO- (CH Si(CH )(OC I-I and3-chloro-3-cyanopropylmethyldiethoxysilane Further distillation yields asecond higher boiling fraction (fraction 2).

Infra-red analysis indicated that fraction 2 is a mixture of 3-chloro 3cyanopropylmethyldiethoxysilane NC- (OC2H5)2 and 3,3-dlCh1D1'O'3'cyanopropylmethyldiethoxysilane NC--CC1 (CH Si(CH (OC H 2 EXAMPLE 7 Intoa one-liter, three-necked flask fitted with mechanical stirrer,thermometer, condenser, and dropping tunnel was placed 224 g. (1.0 mole)of 2,2-dichloro-2-cyanoethyltrichlorosilane The system was evacuated toabout 90 mm. of Hg pressure. Ethanol, 138 g. (3.0 moles) was addeddropwise with vigorous stirring over 30 minutes, maintaining thetemperature below +5 C. by means of a solid carbon dioxide-acetone bath.The mixture was then stirred for 2 hours while warming to 25 C. andfinally to 80 C. over 20 minutes with pressure reaching 90 mm. Themixture was charged to a 1-liter distillation flask and distilled toyield 167 g. of a product, B.P. 75 /1.0 mm. Hg, 68/0.5 mm. Hg, n 1,4293,

Fractional distillation of the product gave pure 2,2-dichlo-ro-2-cy-anoethyltriethoxysilane EXAMPLE 8 Into a 2-liter,three-necked flask fitted with mechanical stirrer, thermometer, droppingfunnel and condenser connected to a water aspirator was placed 521 g.(2.36 moles) of 2,2-dichloro-Z-cyanoethyltrichlorosilane The system wasevacuated to approximately mm. of Hg pressure and triethylorthoformate,1 g. (7.32 moles) was added dropwise at room temperature with vigorousstirring over 1 hour. The mixture was heated to 75 C. for 1 hour. Thelow boiling by-products of the reaction were removed by vacuumstripping. The reaction residue was distilled at reduced pressure toyield 2,2-dichloro-Z-cyanoethyltriethoxysilane (B.P. 85 C./1.5 mm. Hg; n1.4294).

The structure of 2,2-dichioro-2-cyanoethyltriethoxysilane was verifiedby infra-red analysis.

EXAMPLE 9 Z-cyanoethyltrichlorosilane (205 g., 1.09 mol.) and ferricchloride (2 g.) were charged into a 500 ml. flask fitted with a gasinlet tube, thermometer and gas outlet tube. Anhydrous hydrogen chloridewas bubbled into the contents of the flask for 10 minutes atapproximately 25 C. A weight gain of 3.6 grams, due to dissolvedhydrogen chloride, was observed and a clear yellow solution wasobtained. Chlorine gas was then bubbled into the solution for a total oftwo hours in the presence of diffuse sunlight. The temperature of thereaction was from 35 C. to 55 C. During the chlorine addition thesolution became red. When the solution turned red the chlorine additionwas discontinued and the solution treated with anhydrous hydrogenchloride until the solution turned yellow. After the chlorine additionwas completed (2 hours total addition) the solution was distilled underreduced pressure to yield 223 grams of a mixture ofpolychloro2-cyanoethyltrichlorosilanes said mixture collected as adistillate boiling in the range of 43 C. at 0.25 mm. Hg to 86 C. at 0.9mm. Hg, n =1.4730 and 55.5% hydrolyzable chlorine.

What is claimed is:

1. As a new composition of matter an organosilicon compound containingat least one silicon-bonded chlorocyanoalkyl group of the formula:

groups, and (2) organosiloxanes having all of the valences of thesilicon atom containing the chlorocyanoalkyl group, other than thevalences satisfied by said chlorocyanoalkyl group and by siloxanelinkages, satisfied by a member of the class consisting of methyl groupsand phenyl groups and all remaining valences of silicon of saidorganosiloxane being satisfied by monovalent hydrocarbon groups.

2. As a new composition of matter chlorocyanoalkylsilanes of theformula:

f!!! NO (0 ,mon) usiXi-m,

wherein R is a member of the class consisting of methyl groups andphenyl groups, X is selected from the class consisting of chlorine,fluorine and alkoxy groups, (a) is an integer of from 2 to 12, (b) is aninteger, (c) is an integer of at least 1, the sum of (b+c) being equalto 2a, (11) is an integer from 1 to 3, (m) is an inte er of from [1] 0to [3] 2 and the sum of (m-J-n) is from 1 to 3.

3. As a new composition of matter a chlorocyanoalkylsiloxane containingat least one unit of the formula:

1 NO onnomnsio wherein R is a member of the class consisting of methylgroups and phenyl groups, (a) is an integer of from 2 to 12, (b) is aninteger, (c) is an integer of at least I, the sum of (b+c) being equalto 2a, (n) is an integer of from 1 to 3, (m) is an integer of from [1] 0to E3] 2, and the sum of (m+n) is from 1 to 3, and at least one unit ofthe formula:

wherein R is a monovalent hydrocarbon radical and (d) is an integer offrom 0 to 3.

5. 2-chloro-2-cyanopropyltrichlorosilane.

6. 2chloro-2-cyanopropyltriethoxysilane.

7. 2-chloro-2-cyanoethyltrichlorosilane.

8. 3-chloro-3-cyanopropylmethyldichlorosilane.

9. 2,2-dichloro-2-cyanoethy1triethoxysilane.

10. A process for the production of chlorocyanoalkylsiianes of theformula:

12 NC (O HbCl nSi l-(m-l-n) wherein R is a member of the classconsisting of methyl groups and phenyl groups, Y is selected from thegroup consisting of chlorine and fluorine, (a) is an integer of from 2to 12, (b) is an integer, (c) is an integer of at least 1, the sum of(b-l-c) being equal to 2a, (n) is an integer of from 1 to 3, (m) is aninteger of from [1] 0 to [3] 2 and the sum of (m-l-n) is from 1 to 3which, comprises reacting a cyanoalkylchlorosilane of the formula:

Rm NO (OuHZu) nS iYi(m+n wherein R, Y, (a), (m) and (n) are as abovedefined, with chlorine in the presence of ultraviolet light andanhydrous hydrogen chloride.

11. A process as claimed in claim 10 wherein the reaction is conductedin the presence of ultraviolet light, anhydrous hydrogen chloride andferric chloride.

References Cited in the file of this patent or the original patentUNITED STATES PATENTS 2,907,784 Iex et al Oct. 6, 1959 FOREIGN PATENTS1,116,725 France Feb. 6, 1956 1,116,726 France Feb. 6, 1956 1,118,500France Mar. 19, 1956

